Cyclo[9]pyrrole: Selective Synthesis of [34]Nonaphyrin(0.0.0.0.0.0.0.0.0)

Abstract

Cyclo­[9]­pyrrole, a ring-expanded porphyrin without meso-bridges and having an odd number of pyrroles, was synthesized via the oxidative coupling of 2,2′:5′,2″-terpyrrole. X-ray crystallography showed a C 2-like symmetry with a large root-mean-square deviation. The optical properties and electronic structures were analyzed using magnetic circular dichroism spectroscopy and time-dependent density functional theory calculations.

Mono- and bis-Pd(ii) complexes of N-confused dithiahexaphyrin(1.1.1.1.1.0) with the absorption and aromaticity modulated by Pd(ii) coordination, macrocycle contraction and ancillary ligands

“…To assess the planarity of the macrocycles, the root mean squared deviation (RMSD) values for all the atoms in the macrocycle can be calculated from the crystal data as a quantitative index. 72,73 As a result, the RMSD value of 1 was calculated to be 0.404 Å, similar that of 0.402 Å obtained for the corresponding all-pyrrole hexaphyrin(1.1.1.1.1.0). 74 Upon coordination of Pd(II) in the cavity composed of A, B, C and F rings, the RMSD value of 2 was calculated to be 0.319 Å, indicating that the coordination results in enhanced planarity.…”

Confusion Approach Modulated Syntheses of Corrorin Parasitized Hexaphyrins(1.1.1.1.1.0) and the Oxidative Ring Cleavage Behavior

“…As a result, no global aromaticity is observed for 1 . To further assess the planarity of the hexaphyrin unit in 1 , the root mean squared deviation (RMSD) for all the 35 C and N atoms involved in the macrocycle was calculated to be 0.528 Å, obviously larger than that of 0.402 Å for the nonparasitized hexaphyrin(1.1.1.1.1.0), indicating that the hexaphyrin unit in 1 is more distorted than the corresponding nonparasitized structure. Notably, the H1 atom within the corrorin unit is hydrogen-bonded to N2 with the N1···N2 distance of 2.485 Å, which is consistent with the NMR data.…”

Pd(II) and Cu(III) Complexes of Multiply Fused Pentaphyrin Isomers with Tunable Structures and NIR Absorption

“…The crystal structure of 3 reveals a rearranged macrocycle composed of a nearly coplanar [5.6.6.5.7.5]-hexacyclic fused segment, which tilts from the dipyrrin unit D–E with a small dihedral angle of 13.2° (Figure c,d). The root-mean-square deviation (RMSD) , for all the C and N atoms of the macrocyclic skeleton was calculated from the crystal data as the quantitative index to further evaluate the planarity. The RMSD value obtained for 3 (0.277 Å) lies between those of 1 (0.319 Å) and 2 (0.235 Å), indicative of a roughly planar structure of 3 similar to those of 1 and 2 .…”